Diels-Alder reactions of A cage-annulated cyclohexa-1,3-diene. Synthesis and crystal structure of A doubly-caged sterically-congested tetraol

Revealing the Origin of Π‐facial and Regioselectivity in the Diels‐Alder Reaction of Unsymmetrical, Cage‐annulated 1,3‐Cyclohexadiene with Ethyl Propiolate Dienophile: a DFT Study

“…[8][9][10][11][12][13][14][15][16] The Diels-Alder reactions of π-facially differentiated cage-annulated 1,3-dienes are well-studied and have received attention from organic chemists. [17][18][19][20][21][22][23][24][25] The cycloaddition reaction of hexacyclo [7.5.1.0 1,6 .0 6,13 .0 8,12 .0 10,14 ] pentadeca-2,4-diene-7,15-dione (HPDD) with ethyl propiolate (EP) was reported to give a mixture of two isomeric cycloadducts with a high degree of π-facial selectivity and the cycloadduct formed by syn-π-facial attack of EP to HPDD is obtained as a major product. (product ratio, syn:anti = 80 : 20) [Scheme 1].…”

“…The Diels‐Alder reaction has been utilized for the formation of various agrochemicals, natural products, biomaterials, and other hetero‐aromatic compounds [8‐16] . The Diels‐Alder reactions of π‐facially differentiated cage‐annulated 1,3‐dienes are well‐studied and have received attention from organic chemists [17‐25] . The cycloaddition reaction of hexacyclo [7.5.1.0 1,6 .0 6,13 .0 8,12 .0 10,14 ] pentadeca‐2,4‐diene‐7,15‐dione ( HPDD ) with ethyl propiolate ( EP ) was reported to give a mixture of two isomeric cycloadducts with a high degree of π‐facial selectivity and the cycloadduct formed by syn ‐π‐facial attack of EP to HPDD is obtained as a major product.…”

Theoretical investigation on facial and stereoselectivity in Diels‐Alder cycloadditions of maleic anhydride to dissymmetric cage‐annulated cyclohexa‐1,3‐dienes

“…In the present work, we have performed a theoretical study on mechanism of the P‐DA reaction of cage‐annulated cyclohexa‐1,3‐diene 10,12,13,14‐tetrachloro‐11,11‐dimethoxy‐hexacyclo [7.5.1.0 1,6 .0 6,13 .0 8,12 .0 10,14 ]pentadeca‐2,4‐diene‐7,15‐dione (TDPDD) with maleic anhydride (MA) (Figure ) experimentally studied by Chou et al…”

A DFT investigation of Diels-Alder reaction of ethyl propiolate to the cage-annulated hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione

“…The Diels-Alder (DA) reactions of cage compounds with facially differentiated 1,3-diene moieties have been the subjects of extensive studies in recent years. [1][2][3][4][5][6][7][8] Cage-fused cyclohexa-1,3-dienes are widely used for this type DA reactions as very useful substrates due to the absence of conformational uncer-838 ATALAY and ABBASOGLU tainties in its structures. Isolated cases of such reactions of some dienophiles with a π-facially differentiated cyclohexa-1,3-diene, e.g., hexacyclo-[7.5.2.0 1,6 .0 6,13 .0 8,12 .0 10,14 ]hexadeca-2,4-diene-7,16-dione (HHDD) 9 have been studied.…”

“…[1][2][3][4][5][6][7][8] Cage-fused cyclohexa-1,3-dienes are widely used for this type DA reactions as very useful substrates due to the absence of conformational uncer-838 ATALAY and ABBASOGLU tainties in its structures. Isolated cases of such reactions of some dienophiles with a π-facially differentiated cyclohexa-1,3-diene, e.g., hexacyclo-[7.5.2.0 1,6 .0 6,13 .0 8,12 .0 10,14 ]hexadeca-2,4-diene-7,16-dione (HHDD) 9 have been studied. Herein a related study of the DA cycloaddition reaction of ethyl propiolate (EP) to caged diene HHDD is reported.…”